vu BA MINH EBOOKBKMT.COM Tai liu ky thuat miée phiDAI HOC QUOC GIA TP H6 CHi MINH TRUONG DAI HOC BACH KHOA Va Ba Minh EBOOKBKMT.COM ‘Tai ligu ky thuat miéo phi QUA TRINH VA THIET BI CONG NGHE HOA HOC VA THUC PHAM TAP 4 KY THUAT PHAN UNG (Téi ban lan thit ne) NHA XUAT BAN DAI HOC QUOC GIA TP HO CHi MINH - 2013EBOOKBKMT.COM Tai ligu ky thuat miéa phi MUC LUC Loi noi déu Chuong 1 KHAI NIEM M6 DAU 1.1 Dong héa hoe 1.2 Nhiét dong lye hoe 1.8 Phan loi phan dng 1.4 Dinh nghia van téc phan tng 1.5 Phan logi thiét bi phan ting Bai tap chuong 1 Chuong 2 XU LY DU KIBN BONG Hoc 2.1 Thiét bi phan img gidn doan c6 thé tich khéng adi 2.2 Binh phan ting gian doan c6 thé tich thay aéi 2.8 Nhiét do va van té: phan ing Bai tap chuong 2 Chuong 8 PHUONG TRINH THIET KE 3.1 CAn bang vat chdt va nang lugng téng quét 3.2 Thiét bj phan img Khudy tron ly tudng 3.3 Thiet bi phan ing dang tng Bai tap chuong 3 Chuong 4 AP DUNG PHUONG TRINH THIET KE 4.1 So sinh kich thudc thiét bi phan dng don 4.2 He ohiéu binh phan dag 4.3 Thiét ké cho phan sing da hgp Bai tgp chuong 4 10 12 w 19 24 26 31 32 48 51 BT 59 60 61 es 87 22 ot 101 107 127}OKBKMT.COM Kp thud mide phi Chuang 5 HIEU UNG NHIET BO 5.1 Khai nigm vé higu tng nhiét do 5.2 Binh khudy tron ly tuéng hoat dong én dinh 5.3 Binh khuay tron ly tuéng hoat dong gidn doan 5.4 Binh khudy tron ly tuéng hoat dong ban lién tuc 5.5 Thiét bj phan img dang éng 5.6 Khoang nhiét do t6i uu Bai tap chuong 5 Chuong 6 DONG CHAY THUC 6.1 Khai niém vé khudy trgn va mé hinh 6.2 Su phan bé thdi gian lun cita lu chat trong binh 6.3 Cae phuong phép thye nghigm 6.4 Sit dung ede théng tin phén phéi thei gian hm 6.5 Xéc dink d9 chuyén hea truc tidp tir thuc nghiém 6.6 Mo hinh cho dong chay thyc 6.7 Kat lua Bai tap chuong 6 Chuong 7 DAI CUONG VE THIET KE HE PHAN UNG DI THE 7.1 Phan loai hé phan img di thé 7.2 Phuong trinh van t6e cho phan tng di thé 7.8 Céc mé hinh tiép xc pha Bai t€p chitong 7 Chuong 8 PHAN UNG RAN - LUU CHAT KHONG XUC TAC 8.1 Cae khéi nigm vé thist ke 8.2 M6 hinh phan ing 8.3 Van tée phan tng theo mé hinh 10i chua chuyén héa 8.4 Van téc phan img vdi hat cdu co rit 130 130 131 138 139 143, 143 162 166 167 168 169 172 175 178 200 201 203 203 204 209 210 212 213 214 2228.5 Xdc dinh tré luc kiém sodt van tée 8.6 Ap dung vao thiét ké Bai tap chuung 8 Chuang 9 PHAN UNG LUU CHAT - LUU CHAT 9.1 Phung trinh van téc 9,2 Ap dung vao thist ké Bai tap chung 9 Chuang 10 PHAN UNG SUC TAG CHAT RAN 10.1 Khai niem 10.2 Hap phu trén bé mat chat réa 10.3 Phuong trinh van téc 104 Phuong phap thye nghiém dé xée dinh van t6c phan img 10.6 Phan phéi sin phdm trong phan tng da hop 10.6 Ap dung vao thiét ké Bai tap chutong 10 Chuang 11 PHAN UNG SINH HQC 11.1 Qué trinh 1én men enzym 11.2 Qué trinh men bing vi sinh 11.3 Qué trinh lén men vi sinh do co chat kiém sodt 11,4 Lén men vi sinh do san phaém kiém soat Bai tap chuong 11 Tai lau tham khdo 224 230 247 250 251 267 290 294 294 297 298 314 322 834 347 349 350 358 363 372 378 380EROOKBKMT.COM ‘Tai ligu ky thuat mién phi Loi noi déu KY THUAT PHAN ONG Ia tdp thit tu trong 66 séch QUA TRINH VA THIET BI CONG NGHE HOA HOC VA THUC PHAM do cdc edn b6 gidng day BG mén Mdy va Thiét Bj Khoa Cong ngh@ héa hoe vd. Du khi Truong Dai hoc Back khoa — Dai hoe Quée gia Thanh phé Hé Chi Minh bién sogn. Noi dung cuén sdch dugc bién soan dya theo dé cuong chuong trinh mén Ky thudé phdn ung déng thé va ky thuat phan tng dj thé cia Khoa Céng nghé héa hoe va Ddu kht Truang Dai hoc Bach Khoa — Dai hoe Quéc gia Thanh pho Hé Cht Minh. , Cuén séch tép trung trinh bay nhitng vdn dé co ban vé quad trinh va thiét bi phdn tng cd déng thé lan di thé, gici thigu mét s6 phuong phap thiét thue dé tink todn va thitt ké thidt bj phan ng, c6 nhiéu vi dy mink hoa. Ngodi vide ding lam tai ligu gidng day va hoe tap eda sink vien Truéng Dei hoe Bach khog va ede truong dai hoe, eao ding khac cé déo teo nganh Héa - Thue phém, cuén sdch nay con la tai lidu tham khdo cho ede cdn BG RY thud od lien quan dén link vue nay. Dy la cudn sdch dugc in va tai bdn e6 sita chita nhiéu lan. Tuy nhién téc gid vdn rét mong nhgn duge nhiéu y kién dong gép cua ban doe. Dia chi lien h@:, BG mén May va Thiét bi Khoa Céng nghé héa hoc va Dau khi Truong Dai hoc Bach khoa ~ Dai hoc Quéc gia Thanh ph Hé Chi Minh BT: (08)8650484; (08) 8647256 - 5680. Tac gid ‘Va Ba MinhEBOOKSKMT.COM Tai liéu ky thuat miéo phi Chuong 1 KHAI NIEM M6 DAU M&i mét qui trinh céng nghé héa hoc duge thiét ké nhim dé sao xudt mét cach kinh té mét sdén phdém mong mudn tiv cdc nguén nguyén ligu khée nhau qua mét sf céng doan xit ly néi tiép nhav. Hinh 1.1 cho thay mét trudng hop tng quat. - Nguyén ligu trai qua mét sé céng doan xit ly vat ly dé tao thanh dang thich hgp cho céng doan phan ting héa hoe. - San phdm eda céng doan héa hoe sé trai qua cdc cong doan xif ly vat ly tiép theo (phan tach, tinh ché...) dé dat duge san phém cudi cing theo nhing tiéu chudn mong mubr Dong hoa lu Hinh 1d: Qui trinh céng nghé héa hoc téng quat Trong cuén séch nay ta chi quan tam dén cing doan phan tmg héa hoc. Thiét ké thiét bi phdn tng khéng phai 1a céng viée theo mét ichuén mau 6 s&n, ma thuong 1a c6 thé gém nhiéu ban thiét ké khée nhau cho mét qui trinh. ‘Thiét ké téi uu phai dya trén tinh kinh t& eda toan bd qui trinh chit khéng phai chi dya trén mét thiét bi phan ung. Dé thiét ké mot thiét bi phan ung ta phdi of kién thite va sd ligu thuge nhiéu linh yye kh4e nhau nhu: nhigt dong lye hoc; dong hoa hoe; ca hoe lu chét; truyén nhiét; truyén khdi; kinh té. Ky thuat phan ding héa hoc 1a sy téng hop cdc yéu td thude ede link vue tran nh&m mye dich thiét ké dung din mét thiét bj phan ting.10 CHUONG t Trong viée thiét ké thiét bi phan Ung, hai c4u hdi sau phai duge tra loi: 1- Ta muén phan tmg nao xdy ra? 2. Téc 46 cia phan img dé nhu thé nao? Cau héi 1 lién quan dén nhiét dong lyc hoc, céu héi 2 lién quan én céc qué trinh van téc nhut déag hoa hoc, truyén nbiét, trayén kbéi.... Dé lién két ching lai véi nhau va xc dinh xem ching 6 quan hé tuong hé nhu thé nao 1a mot bai todin cue ky khé, Tuy nhién, ta sé bat dau céng viée bing nhiing trutng hop don gidn nhét va sau do dn lugt xem xét ede yeu té bd sung cho dén khi dat duge mét lai gidi hoan chinh cho bai todn. Sau day ta sé xem xét van tat hai tinh wc lién quan I d6ng héa hoe va nhiét dong lye hoc. 1.1 DONG HOA HOC Dong héa hoe la mon hoc nghien. citu te dé phan ung héa hoc va co ché ma theo dé mét phan ung héa hoc sé xdy ra. Trong viée thiét ké thiét bi phan img ta cdn phai biét dén phuong trinh vén tde phan ting thich hyp. Co ché phan ting chi can thidt khi ta suy di&n cde 86 ligu van tée vugt qué cde thi nghiém ban dau, va trong vide khéi quat héa déng hoc phan ting Sau day 1& tém tt mob 96 Ichai niém lién quan. I- Phan ting don va phan ting da hop Phan mg don 1a phan wing chi cdn mot phuong trinh lygng héa hoc va mét phuong trinh vén tc 46 biéu dién qué trinh phan (ing. Phan ting da hgp la phén dng phai cdn hon mét phuong trinh lugng héa hoc va phuong trinh van téc 48 bigu dién qua trinh phdn ing. Phan tng da hop chia ra lam: Phan tng néi tiép Am RS Phan img song song A —». RB; AS Phin inghénhgp A+B —» R; R+B—S 2 Phan ting so déng va phdn ting khong so dang X6t mot phan tmg don c6 phuong trinh lugng héa hoe: A+tB—+RKHAI NIEM MO DAU Ai. Phan (tng so dang la phan tmg xay ra trong mét giai doan theo thuyét va cham va phuung trinh van tée duge suy ra tif phuong trinh lugng héa hoe: (rq) = REACa Negugc lai, khi khong cé sy lién hé gida phuong trinh lugng héa hoe va phuong trinh van tée ta goi la phan ting khéng so dng. Vi dy phan ting gitta hydrogen va brom: Hy + Bry —» 2HBr hOn08 a inh t6e 1A = of phuong trinh wan 16 18 (tam) = eG 3. Can bang cho phan tng thudn nghich so déng Xét phan ting thudn nghich so ding: A+B ee R+S ‘Van tée phan ung thufn: (rp), = mCaCp ‘an téc phan ung nghich: (rg)ng =— heCrs G diéu kién cén bang khong 06 sy thanh lap R: Cee, =0, hay 2 Gels Cady *Uadng =9, hay Fh= oh Cpls vi Ke duge dinh nghia la Ky = eo aCe Cpe; nen Ko= 7 = Geen tne 4- Bac phan ting Cho phan ting 6 phuong trinh van t6c 1a: Cra kCGCR..Chi a+ b+..+d=n (1.1) (1.2) (1.3) véi a, b, ..., d khong nbat thiét la cdc hé s6 cla phyong trinh Ivong héa hoc. Nhu véy phan dng 1A: Bac @ theo tae chat A Bac b theo téc chat B Bac n 1a bac téng quat. Bac phan tng khong nhét thiét phi la 96 nguyén.12 CHUONG 1 5- Si tity thugc nhiét dé cia phuong trinh van tée Theo dinh lw4t Arrhénius, phuong trinh vén téc phan ting: (=n) = kf (néng do) voi k la hing sé van tc phan ting duge biéy dién theo dinh Inat Arrhénius: hes ke E RT (14) voi: k,- thita sd tdn 96; E - nang lugng kich dong cia phan tng. 1.2 NHIET BONG LUC HOC Nhiét dng lye hoe cho ta biét hai didu cén thiét cho viée thiét ké Ja nhiét phong thich, hode nhiét duge hap thu trong qué trinh phan tng, va muc d$ phan tng t0i da cé thé dat duge néu la phan ting thudn nghich. I- Nhigt phan ting Nhiét phan ing la nhiét phong thich hodc hdp thu bdi phan ung, bhi phan ting duge qui vé nhigt dé cila tae chat. Néu dp sudt khéng déi, nhiét phan dng bing vdi sy bién déi enthalpy. Nhiét phan ting 6 thé duge tinh ti nhiét cdu tao va nhiét dét chdy cfia sin phém va téc chat. Khi khong cé sé ligu thuc nghiém cé thé tinh theo phuong ph4p cia Hougen va Watson cho ede hep chat chia carbon, hydrogen, oxygen, nitrogen, va cdc halogen. Khi can tinh nhiét phan tng ohiét 46 T, theo nhiét phan ving é nhiét do T,, ta 06: r AH,» = AH, + Ja6,aT (1.5) % vei: AC, = EON,C pi) ~INCoi re (1.6) Néu biét nhigt dung riéng trung binh C, trong khodng nhiét 43 T, va T, thi (1.5) duge vist 1a: BH, p = AH, 7, + EN {Cpi)yy(T-T,)-2(N,Cpi),(T-T,) (1.7) Anh huéng cia 4p sudt trén nhiét phan tmg cia cdc ch4t khi toy thuge trén su sai léch so vdi khi ly tudng cla cdc cdu tit nay. Néu tacKHAL NIEM MG BAU 13 chat va sin phém 1a khi ly tuéng thi 4p sudt khéng ¢6 anh hung. 2. Can bang héa hoc Khi phan tug 6 trang thai cAn bang, nhigt dO va 4p suat eda hé gid khong adi, ay bién Adi nang lugng ty do bing khong thi tiy dé ta c6 suf lién hé gitia su bin ai nang lugng tu, do chudn AF? ya hing 86 can bing K: AF? = - RTInK . (1.8) v6i AF® 1a higu s6 gitia nang lugng ty do cia sdn phdm va tac chat & diéu kién chudn. Trang thdi chudn duge chon sao cho tinh nang lugng tu do don gidn nhdt. Hang 36 cin bing K duge dinh nghia theo hoat 4 can bang a; cila the chat va sin ph4m. Véi phdn ting téng quat: aA+bB —» 7rR+sS (1.9) hang sf cn bing 1a: of Sats (1.10) a4.0 Hoat 46 4 digu kien can bang duoc dinh nghia 1a tl 36 cia fugacity trong hn h¢p can bang véi fugacity trong trang thei chuén. # qb voi phan ting ¢ thé khi e6 fugacity é trang théi chudn bang mét, bidu thie tinh hang sé e&n bang la: K= ffs (1.12) Ngoai ra néu chét khi 1a khf ly tuéng, fugacity bang véi 4p suat riéng phan, phuong trinh (1.12) tré thanh: K = PRPh (1a) PPh va p; = Pry 1p aust riéng phan cia cau tif i trong hn hgp y6i: y, -phén mol; P, - 4p suét ting, ‘Trong nhiéu truéng hop, néu khéng gid sit duge 1 khf ly tuéng th) khi dé can phai tinh fugacity. Vi dy truing hop téng hgp amoniac14 GHUONG 1 vdi 4p suat lam viée cé thé lan dén 1500at. Fugacity trong (1.12) la fugacity cba cau ti trong hén hgp can bang. Dai lugng nay lién hé véi fugacity cia cdu ti nguyén chat theo: R= fi (1.44) ‘Thay biéu thic nay vao (1.12) cho ta bidu thic tinh hang s6 can bing theo fugacity cia cde cdu tt nguyén, chat va thanh phan cia hin hop 6 trang thai can bing. fp)" Fe) =e (1.15) nee? trong d6: K, = 2h . (1.16) ASB Trong cée phn ung & pha khi thudng sit dung dai lugng K,. Dai lugng nay duge dinh nghia la: — GRP shY K, pier (or) aap FAP Pee” So sdnh véi (1.18) ta théy K=K, cho hin hgp phan cing 1a khi ly tudng. Véi hén hyp phan ding 1a khi thye, (1.17) duge ding dé tink K, tit cde thanh phdn can bing. Khi do K, khong bing K duge tink theo (1.8) Phuong trinh (1.17) ding dé tinh K, theo hing sO can bing. Day 1a giai dogn cén thiét dé tinh 46 chuyén héa cdn bang tif s6 ligu nang lugng ty do. C4e bude tinh toan nhu sau: 1- Tinh gid tri AF° 2. Tinh hing 86 cfin bing K ty (1.8) 3 Tinh Ky tit (1.16) 4- Tinh 46 chuyén héa ti K,, Phucng trinh Van’t Hoff biéu dién su bién thién cla hang s6 cin bang theo nhiét 9. d(ink) | Ha, ar RT® v6i AH?y, 1A sy bin thién enthalpy cia phan tng 6 digu kién chudn. (1,18)KHALNIEM MG BAU 15 Phuong trinh (1.18) déng vai trd quan trong trong vige thiét ké cho ede phan tng thuan nghjch. N6 cho thay K gidm theo sy tang nhiét d6 cho phan ung phat ahigt, Tuong tu cho phan dng thu nhiét, K gidm khi nbidt d@ gidm. Khi AH?,, 0c l4p voi nhiet 49, dang tich phan cia (1.18) 1a: : (1.19) Néu AH?y khong la hing 86 mA duge biéu dién theo phuong trinh (1.5), dang tich phan la: AHra, | Aa Ab y' Ac ste 4 Oe pe leg i RT + B InT + +R +€ (1.20) véi: AHP, ,C va da, Ab, Ac- cdc h&ng 26; Aa, Ab, dc tir bidu thie: AC, = Aa+AbT +A0T? (2) Vi du 11: Ethylen oxid duge sén xudt bang each oxy héa trye tigp ethylen vdi ch&t sic tée (bac vA chat mang thich hgp) trong dong khong chi. Gia sit dong nhap ligu vao thiét bi phan ung 4 200°C va chita 5% mol ethylen, 95% mol khéng khi. Néu nhi@t 46 dong ra khéng duge vugt qué 260°C thi d@ chuyéa héa efia ethylen thanh oxit 1a 50% va 40% ethylen bi chéy hoan toan thanh dioxid carbon. Héi phai truyén nhiét ra méi trudng ngoai 1a bao nhiéu cho méi mol ethylen trong nhap ligu dé nhiét 4 khong vugt qué nhigt 43 giéi han. Nhiét dung riéng mol trung binh ctia ethylen 1a 18cal/gmol °C gitta 25 va 200°C va 19caligmol°C gitta 25 vA 260°C , tuong ty cho ethylen oxid 1a 20 va 21cal/gmol°C. Ap suat bing 4p sudt khi quyén. Giai: Vi higu img nhigt 6 ap sudt khong déi bing vdi sit bién adi enthalpy nén qué trinh thyc duge thay bang ede qud trinh sau: 1. Lam ngudi tac chat va khong khi tir 200°C xu6ng 25°C 2. Thye hién phan tg & 25°C 3. Bun néng san ph4m va khong khi ti’ 25°C Jén 260°C Téng 26 bién déi enthalpy cia ba giai doan cho ta hiéu tng nhiét.16 CHUCING 1 Giai doan 1: Trén can ban 1 mol ethyien, sé cd (1} 95/5 = 19 mol khong khi di vao thiét bi phan ting, Nhiét dung riéng trung binh cia khong khi tir 25 dén 200°C 1a 7Wentigmol °C. Vay: AH, = 1018)(200 — 2) +19(7,0)(200 - 25) = 26425 callmol Giai doan 2: Hiéu ing nhiét do 6 hai phan ting: CH, +40, — CH, CyH, +30, —» 2CO, +H,0(k) Ding s6 ligu nhiét edu tao cho 6 bang 1.2 tinh cho phan ting 1: AH, = ~12190 ~ 12496 — 0 = 24686 cal/mol phan tng 2: AH, = 2(-57798) + 2(-94052) — 12496 - 0 = -316.196 cal/mol ‘V6i méi mol ethylen 06 0,5 mol phan ding tao thanh ethylen oxid va 0,4 mol chéy hoan toan nén: Ay, = 0,5(-24.686) + 0,4(-316,196) = —138.821,4 cal/mol Giai doan 3: San phdém gém nhiing cau tir Ethylen = 1- 0,5 - 04 = 0,1 mol Ethylen oxid. = 0,5 mol . Hoi nudéc = 2x0,4 = 0,8mol (€, = 8,25 calfmol’C) Dioxid carbon = 2x0,4=0,8 mol (€p= 9,4 cal/moiC) Nitrogen = 19(0,79) = 15 mol (Cp = 7,0 cal/mol’C) Oxygen = 19(0,21) — 1/2(0,5) ~ 3(0,4) = 2,6 mol (Gy = 6,25 cal/mol’C) Cée gid tri nhiét dung riéng trung binh lay gitta 25 va 260°C: AH, = {0,1(19) + 0,5(21) + 0,8(8,25) + 0,8(9,4) + 15(7,0) + 2,6(7,25)] (260 - 25) = 150 (260 — 25) = 35250 cal/mol. Vay t6ng lugng ohiét lién he 1a: Q = 26425 — 138821,4 + 35250 = — 77146.4 callmol Lugng nhiét phai lay ra khdi hé 1a 77146,4 calfmol ethylen dua yao thiét bi phan Ung.KHAINIEM MO DAU 7 Vi du 1.2: Sé liu e4n bing cho phan img hydrat héa ethylen thanh ethanol trong pha hoi; d 145°C, K = 68x10; & 820°C, K = 1,9x10°. Tit so liu nay tim diéu thie téng quét tinh K theo nhiét d6. Gidi: Tu hai gid tri cia K ta tinh duye AH.» va C theo (1.20). Trude tién tinh Aa,Ab va de tit sé ligu nhiét dung riéng. Vi phan ting: CoHa¢4) +20) —e CoHOF ay ta cé: A=CjH,OH-C,H,-H,O Aa = 6,990 - 2,830 —7,256 = -3,096 ‘Ab = 0,039741 - 0,028601 -0,002298 = 0,008842 bc = (11,926 + 8,726 -0,283)x10° = 3,488x10° Thay cdc gid tri da biét vao (1.20) ta duge: Tai nhiét db 145°C (418K) AH, 7, — 25 _ OR =-Rin(6,8x10)-3,0961n418 418 +0,00442(418) — 0,580x 10*)(418)* = -11,59 (A) Tai nhigt dg 320°C (593K) A, 3 peg OR = ~Rin(1,9x10%)-3,0981n598 +0,00442(598) ~-(0;580x10 °)(593)* = 4,91 (B) Giai phuong trinh (A) va (B) ta duge: AH, 7, =-9460 ealimol va C =-6,56 Thay vao (1.20), biéu thite ting quét tinh K theo T la: InK= 7A -1,s58in 7 +0,002227 0,210" 77 -5,56 Vi du 1.8: Uée tinh dé chuyén h6a t6i da cia ethylen thanh etanol bang phn ting hydrat hoa trong pha hoi tai mbigt d6 260°Cva Sp sudt 34a¢. Dang sf ligu cn bing trong vi dy 1.2 va gid sit ti sé ban du cia hoi nuée va ethylen bing 5. Giai: Fling 86 cn bing K & 280°C duge tinh theo biéu thi eda vi du 1.2:18 CHUONG 1 Ink= a ~1,558 In525 +-0,00222(523) -0,20%10(523)" —5,56 = -5,13 K = 5,9x107 Hon hop khi la kh ly tudng, ép dung (1.16): 59x10° = K, a © fate Cée fugacity cha cde cfu ti nguyén chat duoc xdc dinh tir cdc biéu thie téng quét va tinh gid tri tai nhiét a6 va 4p sudt oda hén hgp can bang: BR thay cdc gid tri trén vao phuong trinh (C), ta duge: K, = ¥B-=5,9x10°8 2.98%0.91, YayE 0 ‘Trén cn ban 1 mol ethylen ban d4u, ean bing vat chat cho két. qua tai diéu kién cfn bing c6 x mol ethylen 4A phan tmg nhu sau: hk 0,84 cho etanol;: & = 0,98 cho ethylen; & 0,91 cho hoi nude * % x34 =0,21 (D) ethanol = 0-2 ethylen = 1-x hoi avge = 5% Téngsd mol = 6-x lox Vay: = + ay: Ya 6-x x(6-x) thay D) ta c6: 0,21 = e788 0 a (1-x)(5-x) Gidi phyong trinh trén véi digu kién x <1, ta duge x = 0,15. Trong phan ting nay nhiét dQ tang sé lam gidém K va 46 chuyén héa. Tang dp sudt sé tang a6 chuyén héa. Theo quan diém can bing, Ap sudt lam viée nén cang lén cang t6t (chi bi gidi han béi qué trinh ngung ty) va nhigt d¢ cang thp cang tét. Chat xic tac cin dé dat duoc tée 46 phan img dang ké nhung cdc chat xtic tac cé thé sit dung déu cdn nhigt d6 t6i thigu 250°C. Tuy nhién didu nay khéng lam tang duge 46 chuyén héa can bang. Trong trudng hop nay do gidi hanKHAI NIEM MO BAU 19 yé d@ chuyén héa cfin bang va van téc phan tng lam cho phan dng khéng cé tinh kinh té, : 1.3 PHAN LOA PHAN UNG C6 nhigu céch phan toai phan ung tuy nhién trong ky thuat phan ung ta quan tam dén s6 pha hién dién trong hé do dé thudng chia cfc phan tg la thanh hai loi: déng thé va di thé. Sy phan loai khéng ré rang véi phdn 1én cfc phan ting sinh hoe, ede phan ting vdi co chat enzym. Bang 1.1: Phan logi phdn ung héa hoc tién Igi cho thiét ké thiét bi phan img Kong xe tae 6 xi tie Hu hat phan dng 6 pha kh Hu hat prn dag & pha ing ‘86ng th Gée phan ding chdy cla ngpn a | Céc phn dng & thé eo Pan dng chy cia than Téng hop amoniac ts ‘Nung quing ‘Oxide n6a amoniae 66 san xutt nitric acid. op Phan ung cla acid vei chi ia Phan cing cracking Hap thy kat -- Fong of phan dng ‘Téng Bgp methanol 1.4 BINH NGHIA VAN TOC PHAN UNG Xét cal tit i trong phan Ung héa hoc. Dua trén ede cin ban khée nhau, ta o6 ede din nghia khde nhau va van téc bién déi cha cdu tid 1én lugt nh sau: - Dya trén mét don vi thé tich hén hop Iw cht phan tmg: pode mol i bidn dé Vi dé — (mét don vj thé tich hén hop phdn ung) (thdi gian) = Dya tron mot don vj thé tich bink phan ding V, (voi V, # Vt »_ 1 dN, mol i bién di (1.28) (1.22) | Dua trén mot dan vj dign tich bé mat tiép xtc pha: »_1dN; _ mol i bién doi 1S "Gt — tnét don vi difn tich bé mat tidp xe phaXthdi gicn) (4.24)20 CHUONG 1 - Dua trén mét don vi khdi lugng chat xc tac (hofec khéi long chat réin trong hé luu chét - chat rain): ~_14N; mol i bién déi of mes TT (1.25) W dt — (mot don vj khdi tuong chat rdn) (thai gian) - Dua trén mét don vi thé tich chat rdn: ~ _ Lan, mol i bién déi (1.26) 1 YS dt Giadt da vj thd tich cht rn) (thai gin) Trong phan ung ding thé, thé tich cia hén hyp phan dng xem nhu bang v6i thé tich cia binh phan ting do dé (1.22) va (1.23) xem la mét. Viée chon dang phuong trinh v4n téc nao dé sit dung trong phan ung di thé tay thuge vao sy dé dang thugn tién khi sir dung. Tit cdc phuong trinh dinh nghia (1,22) dén (1.26) ta ¢6 su lién hé gitta ede téc do phan ting: ¥ (thE tich hin hop phan ting) = 1] (thé tich binh phan ting) = of (dign tich bé mat tiép xtie pha} = r{" Ueh6i Lugng chat rin) = Wf" (thé teh chat rénd 2 (1.27) hay RV = Y= Hf (S)= (WW) = (VD M6t s& phan img xdy ra rat nhanh, mt sé phan img khde lai xdy ra rt cham. Vi dy, trong qua trinh san xuat polyethylen hay qua trinh edn xudt xding ti déu thé, ta mudn phan tng xAy ra rat nhanh, trong int hode vai gidy, trong khi dé trong qué trinh xt ly nude, phan dng xay ra rét cham, trong nhiéu gid hodc nhigu ngay. Do téc dé phan ting thay déi rat nhiéu nén vide thist ké thiet bi phan ting sé rat khde nhau trong nhing truéng hop nay. Céc y€u t6 anh hiiéng dén vén thé phan ting C6 nhiéu yéu té anh hudng dén van téc phan img. Trong phan tmg déng thé rd rang 4p sudt, ahiét do va néng dé Ja cdc bign sé. rong phan tng'di thé do cé hai pha trd én, nén viée truyén vat chat ti pha nay sang pha khéc 14 quan trong, do dé vn téc truyén khéi cing 1a mot bién sé. Véi nhing phin tng e6 phét nhidt hode thu nhiét, téc 46 truyén nhiét anh hudng dén qué trinh phan dng. Do 46, qué trinh truyén nhiét va truyén khéi d6ng vai trd quan trong quyét dinh van téc phan img dj thé.KHAI NIEM MG BAU 21 Trong ede phan tng néi trén, néu phan ting lién hg dén mot sé giai doan xdy ra néi tiép nhau, giai doan chém nhét cé anh hudng lén nhét vA goi 1A giai doan kiém sodt vin téc phan img. Van dé quan trong Ja xée dinh duge ede yéu té anh huéng va mic 46 anh huéng cia cdc yéu té nay Jén giai doan kiém sodt. Chi khi nao ta xdc dinh duoc day 4a cde yéu td anh huéng khi d6 viée suy dién cde két qua trong phong thf nghiém ra thiét ké bi phan ting mdi cé d tin cay cao. Vi du 1.4: Héa chat A duoc bién déi thanh héa ch&t R trong mot thiét bi duge chém bang cac hat vat chém hinh cdu khong réng. Dién tich bé mat riéng cia ch&t xtc tac 18 200m/m® tdng chém, Khéi lugng riéng x6p cia chat xtic tac 1a 2908hg/m'. D8 réng cla tang chém 1a £ = 0,40. . Phuong trinh lugng héa hoc la: A —» 2R vA phuong trinh van t6e phan dng cia A dya trén mot don vi khdéi lugng chat xtic tac 1a: dau (-) cho thay van tée bién déi cia A 14 dm hay A la tée chat a) Viet phuong trinh van téc trén véi don vi ciia ede dai lugng b) Viet phuong trinb van téc (-r), (ra) va Gry). Gidi: a) Don vi ca Cy la mol A/l thé tich rong: cnet oNan mol Aig yt thé tieh ring) _ oe mol A "A=W ag Teg chat ran) Chg oat rdnyth)\ *”T thé tich ring b) Khéi lugng chat xUe tae cho méi don vi thé tich binh phan umg 1a W/V, = 2908 kg/m’ thé tich binh phan tng. Do 46 dua trén mét don vi thé tich binh phan img. Gn) 2-2 oN mot __,_W 1 dNg Wey ta) Vit” @bink phan ingih) V,W dt Vy * L thé tich réng mol A « gt Rel Ec cg OE and (2,908 el Oa de rdnth) 4’ the toch rng to.sp0a— thé tich ring ¢q, __mol A = (0,29 a (1 bink phan. tingith) 1 thé tich réng22 CHUONG 1 D6 réng e= V/V, =0,401 thé tich réngll thé tich binh. Do dé dua trén mét don vi thé tich liu chat 1dN, mol A Yy1dN, VY. Gules As ee ea V dt (lbink phin ingh) VV, dt V 1_Lbink phan dng. 1 thé tich ring mol A } [0,2908. 1 (Cy, ) 0.4 7 thé tich rong ( (bink phan tnghh) ~~“ 'T thé tich rng mol A L thé tich ring Dién tich bé mt riéng cht xue tée cho mét don vi thé tich binh phan tng S/V, = 200m7/m” binb phan ting. Do dé dya trén mét don vi dign tich bé mat ehét aie tac Na mol A Val dN, _V, = (0,72TK) (Ca, 1 : (ery = - SSSA A _ Mh TON Mo) OS 8 dt m™ bb maith) Sy dts. 4 Spann phd Sip paeen on oe inh phn tn 9 995 cs thi tick ring oq, moh A m? bé mat (m@bink phan iingih) “bthé tich ring ‘ : = yasycro'® MPUNE teh rEg, mol A (mabe matin) TIE tick ring Cac hing sé van tée ca -r, va —r, 06 cing thit nguyén; nhung khée ¥ nghia thé tich dua trén d6 van tée phan ting dinh nghia do dé cdn ghi r6 thé t{ch khi dinh nghia van téc cho ede phan ting di thé. Vi du 1.5: Mt dong cd héa tién dét ch4y nhién ligu (hidrogen Iéng) v6i oxigen (oxigen léng). Buéng dot c6 dang hinh try dudng kinh 80cm, dai 75cm va qué trinh chay thay ra 108hg/s khi thai. Néu phan tng chéy xdy ra hoan toan, tim te 49 phan tng cda hidrogen va oxigen. Giai: Thé tich budng dét (hay thé tich hén hop phan ting) trong dé xy ra phan tng chéy (déng thé): V=V= F064 (0,75m) = 0,2121m? Phan tng chy dy ra theo phuong trinh: H, +20, — H,0 Nhut v4y, suét lugng mol nuée sinh ra sau phan cing 1a:KHALNIEM MO BAU 23 Lkmol 108 Agis)(———) = (OBhgis Ee 6 kmolis ‘Theo phyong trinh lugng héa hoe trén, sudt Iugng mol cia Hy va O, tham gia phan dng ehdy l4n lugt 1a 6 kmol/s va 3 kmol/s. Vay tée 46 phan img cia hidrogen va oxigen 1a; 1 kmol 1 (1 __)(-6emots) = 28,29 Ma 2121m* . ms L kimol tp, = _—_} __\(_3kmotis) =14,15 2 221m? ms Vi du 1.6: Mét nguéi can nang 60kg gid sit tidu thy méi ngay luong thule phém cé nang lugng 1a 48004J thye phém hoan toan 1a glucose va xdy ra phuong trink chuyén héa téng quat nhy sau: Cglljp0g+60, —+ 6CO,+6H,O — AH, =2816 kJ Tim téc do chuyén héa chat ciia con ngubi theo mol oxigen tiéu thu/m® con ngudi trong mét gidy (hay kg thé trong). Giai: Téc dO chuyén héa chat theo thé tich con ngudi: og eb No, Oe Vinwi at Theo kinh nghi@m, Ich6i luong riéng cla con nguei 1a p= 100 Ag/m? nén thé tieh ca con ngudi edn nding 60g 1A Vig; =0,06m°. Theo phuong trinh chuyén héa ta 6: No, _¢__4800%Tingdy 6 mol oxigen y_ yy ogmol Oe dt 2816kJImol glucose 1 mol glucose — " ngay a }(-10,28molO,/ngay) = 170,5molO,lan? nga 03 = 0,00197 mol CO, /m.ngay Tée 46 chuyén héa chét theo thé trong: ~h -HG ae ‘Sag 10,23mol Ogingiry) = ,1705 mol Opfkg.ngdy = 1.9710 ®mol Onskg.s24 CHUONG 1 1.5 PHAN LOAI THIET B] PHAN UNG NGi vib phan gia mhibt hoae Cita tnd Hay Jian tye hoac LL sian coan ges, Sia igh lam ngudl Téc onsite Hinh 1.2: Thiét bi phdn ting déng thé hoat déng gidn doan ‘Cita nap tig Hen tyc hoae. alr down Cash knusy —| Lim ngui ita thao tou Wen tus hoae cla dean Hinh 13 Thiét bi phan ing ban lién tne vie ide rn Hinh 1.5: Thiét bi phdn itng xtc tée tdng c6 dink Ni v0ibe prin ‘gia nFigt ho’ Hinh 1.4 Thiét bj phén ting dang dng Hi thal Taisinn hain ung Naphtha va ni roan tau Least Hink 1.6: Thiét bi phan ting wtie téc ting lit héaKHALNIEM MO DAU 25 nap ie. Fp Nhaptiou Nap liou Nmap teu 8 4048 gia ohist Sn phémm hege tam ngUi Hinh 1.7: Binh phan ting khudy tr6n mde néi tiép Thiét bi phan ding cé nhiéu kidu, mdi kigu c6 diéu kién hoat dong khée nhau. Co thé phan loai nhu sau: I- Phén logi theo phitong phap hoat dong - Binh phan ting hoat déng gidn doan, duge dae trung bang su bién déi cia mde 46 phan ting, va tinh chat cua héa hop phan img theo thdi gian. - Binh phan ting hoat dong lién tue, duge dic trung bdi mule a6 phan ting, c6 thé thay d6i theo vj tri nhung khéng déi theo thdi gian. 2 Phan logi theo hink dang cia binh phan tng . ~ Binh Ichudy tron ly tuéng duve dace trung béi tinh chat cda hén hop phan tng déng nhét tai moi vi tri trong thiét bi. - Thiét bi phan tmg dang Ong ly tuéng, dugc dac trung béi cdc phan té ciia luu chat déc 4p véi nhau, mdi phan té 6 ndng dé, nhiét 46... khée nhau, Cée tinh chat nay thay déi theo chiéu dai eda thiét bi 3: Phan loai theo sé pha cia hén hop phan ting - Thiét bj phan tmg déng thé: trong dé hén hgp phdn dng 6 trong mét pha (léng hod khi) - Thiét bi phan dng dj thé: trong dé hdn hgp phén mg hién dién 6 t6i thiéu trong hai pha Gitta bén chat vat 1y cia hén hgp phan ting va loai thiét bj phan ting sit dung cé mét méi lién hé téng quét 1a: phan tng déng thé pha khi thudng duge thyfc hién trong thiét bi dang dng hon 1a dang khudy trén, lién tuc hodc gidn doan; véi phan dng di thé pha léng hodc pha Iéng — rn, c6 thé si dung cd hai loai ing hode khuély tron.26 CHUONG 1 Cade chuong sau déy 6 ldn luot trinh bay: Chuong 2-95: trinh bay cde vn dé vé thiét ké cho phan ting déng thé. ‘Chuong 6: trinh bay dong chay thyc trong céc thiét bj phan ung ly tuéng. Chuong 7 10: trinh bay phan tng di thé. BAI TAP CHUONG 1 14. Co ché phan ting khit etanol ra butadien trong pha hoi gém ba giai doan: (a) khir nude eda etanol; (b) Ikhis hydrogen ca etanol; {c) trimg ngumg etylen va acetaldehyd (a) va (b) cho butadien, C,H. AF° & 400°C cho ba giai doan nhu sau: (a) AF? = -10850 eal/gmol (b) AF = ~3610 cal/gmol ‘ (c) AF® = -1880 cal/gmol Xée dinh d6 chuyén hoa cia etanol thanh butadien 6 400°C, 4p sudt téng cong lat. 1.2. Gid aif ring gid tri eda K, cho phan tmg téng hop methanol 18 9,28x10° 3 laf vA 300°C. Tim gid tri cia cde dai lug sau &.300°C. a) K 6 P, = lat; b) K, 6 P = lat 0) K, 6 PF, =50at; d) K 6 dp suat tong cong 10at va 50at e) K, 2 4p sudt tong cOng 1, 10 va 50at 1.3. Newton, Dodge va Von Wettberg da do thanh phan cia hén hgp can bang gém CO, H, va CH;OH trong phan ung téng hop methanol. Tinh gid tri cla K va AF° & 309°C ti cde sé liéu thie nghiém sau: t = 309°C; P = 170at Thanh phén hén hgp edn bing, % mol, la: hydrogen = 60,9; carbon monoxit = 13,5; methanol = 21,3 1.4. Két qua thyc nghiém trong bai 1.3 nhu sau: sooo. k [16s [x73 [172 [17s | vee [1.81 [ 102 | 182 fog K 4,18 | -3,75 | -365 | -3,30 | -a,10 | -3.20 | -,00 | -2.90 sooo. kK" | 1.83 | tee | 191 | ior | 192 | 205 { 205 | 2.05 jog K =2.95 | -2,60 | -27a | -3.00 | -2,30 | -2.30 | -2,15 { -2.95 Ti sé ligu trén xde dinh méi quan hé gitta K va T theo dang: a Ink = A,5+B ptKHAt NIEM MO BAU a7 Bang 1.2: Nang lueng cdu tao va dét chay 6 diéu kign chudn cho san phdm phan ung la H2O (Y) va COs (k} 6 25°C, calimol chat Cong thie THATS | abana | ~aHE zone ‘Methane CHa k 17.860 | 212.800 Etan oH K “20.236 [372.820 ropan CsHe K =24.820 | 690.600 a= butan Catto K 30.150 | 687.640 nv pentan CsHhe K 35.000 [845.160 = hexan CeHia k =99.960 [1.002.570 Tang mbinguyan HG trén Cy k 4.925 | 157.440 Eiyien CoH K 12.498 | 337.280 Propylene Cote k 4870 | _491.990 1 buten Cats K =30 | 649.450 1 = penten Coto K 5.000 | 806.850 1 = haxen Cette k 5.980 | 964.260 Tang mBi nguyén tC trén Cy K ~4925 | 157.440 ‘Acetaldehiyd CoH k “38.780 Acatic acid CatlyOe 1 116.400 Acatyien CoH k 34.194 | _ 910.620 Benzene Colts k 19820 | 789.080 Bonzone CoHe i 11.720 | 780.980 1,3 — Butadion Cats k 26.930 | _ 607.490 Gyclohexan Cote k 29.430 | 944.750 Etanat GyHgO_ hd 58240 Etanol CHO U 06.356 Eyl benzene Gato k 7.420 | 4.301.420 Eiyton glycol» CaHaOe i =108.580 Efyfon oxide CoH k 12.190 Methanol CHyo k 48.100 ‘Methanol CHO. I =57.086 Metyleyciohexan CrHia K =36.990 | 1.099.560 Matyleyciohexan Cis i =45.450 | 1.091.190 ‘Syren Cele X 35.220 | 1.060.900 Toluen CrHe k 11.950 | 943.560 Toluen He 1 2.870 934.500 | “Amoniac NH k 11.04028 CHUONG 1 chat Céng thie deat AHPoca | ~AH? a9ox Cale carburet CeCe r 4.000 Cale carbonat GaGOs r 268.450 Calel clorur CaCly | = 190.000 ‘Galal clorur CaC.6H20 7 = 623.180 aici hyaroxit CaloHye r | ~ 295.800 Gall oxide Cad 7 | 151.800 Carbon, c graphit 94.052 Carbon dioxtt CO k = 94.052 Carbon monoxide co « Taste | 67.696 Glorhydrie acid Her k_ | 22.063 Hydrogen He. Kk 68.817 Hydiogen sultur HS k = 4815 Ont sdi Feo fi = 64.300 nit sft FegQ, | F - 267.000 ‘Onit sdt Fe203 r = 196.500 ‘Sulfur sat FeSp r = 42.520 Lithiom clorur uct r = 97.700 Lithium cforur LICI.H2O T = 170.910 ‘Lithium etorur LICL 2H20 | -242.100 “Lithium elorur LICL3H2O r = 313.500 ‘Nitric acid HNO3, T = 41.404 ‘Niragen oxide NO k 21.600 NO; k 8041 NO ke 19.460 HeOs k 2,309 ‘Sodium carbonat NazGO3 r__ | -270.300 ‘Sodium carbanat NagCOz.10H,0 | | ~975600 Sodium clorur NaCl r = 98.232 Sodium hydroxit NaOH r ~— 101.990 ‘Sulfur dioxide ‘SO> Kk = 70,960 ‘Sullur trioxide SOs ke — 84.450 ‘Sultur trioxide ‘Oy 1 = 104.800 ‘Sullude ackd 1280 1 = 193.910 ‘Nude H20 K 87.798 Nuc HO ! = 68.317KHALNIEM MO BAU 29 Bang 1.8: Nang luong tu do cdu tao 4 25°C chat Cong thie ‘Trang thai AF 290K wetigne CHa k 712.140 Etan CrHs k = 7.860 Propan SoHo k 5.814 a Bute Catto k = 4.100 ‘a — Penta CoH k = 2.000 n= Hexen Cokin k =70 = Heptan CHyp k 7.920 n— Gotan CoH k 3.920 Tang méi nguyen 1 C wen Co 2010 Etyien Cotte K 18.282 Propylene CHa a 14.890 t= Guten Cite « 17.090 1 = Penten Cotto k 18.960 1 = Hexen Cotte k 20.940 Tang mét nguyén tC wen Oe 2.010 ‘Acetaldahyd CoH40 K = 31.960 ‘Acetic acid CoHtsO2 V = 93.600 Acetylen CoHe ke 50.000 Banzane Cote k 30.989 Benzene Cotte 1 28.756 1,3 ~ Butadion Catto k 36.010 Gyctohexan Getty k 7.590 Cyclohexan SoHy2 1 6.370 Etano! ‘SoH k = 40.300 Etano! aH 1 = 41.70 Ely! benzene Catia k 31208 Eiylen glyco! CoHeQr 1 — 77.420 Etylon oxida CyHyO k ~ 2700 Methanol CH.O k 38.700 Mathanol Hy ' = 39.750 Matyicyiohoxan CrHia k 6.520 ‘Metyicyciohexan Grtig j 4-860 ‘Siyren Cals x 51.100 Taluen Crt k 20.22880. HUONG 1 chat Céng thie Trang thai AF 208K Crt t 27 282 NHs x =3.976 NH3 dd 6.370 Cate r 16.200 ‘alc cerbonat CaCOy r ~269.780 Gach F = 179.00 Galei cicrur CaCl, aa = 194.880 Celci hydroxid CalOH)e , = 214.390 Cale hydroxia SalOHe ad = 207.370 Galci oxige. CaO r = 144.400 Carbon dioxid C02 K = 94.260 Carbon monoxid £O k = 92.808 Glorhydrie acid GE k 22769 Hydrogen sulur H28 k = 7.892 ‘Ont sat FesOu i = 242.400 Oxide sat Fess r = 177.100 ‘Sulfur sat FeSp i = 99.860 Nic acia HINO} 1 = 18.100 Wire acio HNO ad = 26.410 Nirogen oxide NO K 20,719 NOs k 12.390 N20 k 24.760 N2O4 k 23.491 ‘Sodium carbanat NagCO3 c = 280.400 ‘Sodium clorur NaCl = ~o1785 ‘Sodium clorur NaCl aa = 93.930 ‘Satur hycroxid NaOH © = 90.600 ‘Sodium hydroxid Nao ad = 100.184 Sullur dioxid S02 k = 71.790 Sulfur tionid $03 k = 88.520 Sulfuric acid HS, a ~ 177.340 Nude HzO k = 54.605 ute HzO 1 = 56.890